Compositions for binding pigments



having the general formula United States Patent '0 COMPOSITIONS FORBINDING PIGMENTS Benjamin B. Kine, Levittown, and Albert C. Nuessle,Hatboro, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., acorporation of Delaware No Drawing. Application April 14, 1954 SerialNo. 423,241

13 Claims. (Cl. 117-161) Aqueous solutions containing starch andWater-soluble linear polymers have commonly been employed for bindingpigments in pigment-dyeing procedures. They have the disadvantages ofrequiring the use of low concentration solutions or highly viscoussolutions which do not penetrate well. They invariably stiffen thefabric, cause the feel or hand of the fabric to vary considerably withchanges in humidity, tend to yellow on ageing, tend to render the fabricmore subject to bacterial and fungal attack, and tend to poorWash-fastness.

Synthetic linear polymers of the vinyl and acrylic types are capable ofserving as binders for pigments, but generally they are characterized byinsufficient resistance to laundering or washing operations because oftheir tendency to become plastic and exhibit plastic flow to some degreeat temperatures that are normally employed for washing operations.

It is an object of the present invention to provide synthetic resinousbinder compositions for pigments which are free of the disadvantages ofaqueous starch solutions and comprise certain linear polymers ofmonoethyleni- -cally unsaturated monomeric materials which, when appliedto textiles or other objects, are capable of further reaction to producea cross-linked binder characterized with adequate resistance to Washingat the normal temperatures employed for laundering and even forscouring. .Another dbject is to provide colored textile materials whichare resistant to normal dry-cleaning operations. Other objects andadvantages of the invention will be apparent from the descriptionthereof hereinafter.

The improved pigment binding compositions of the present inventioncomprise aqueous dispersions of a "water-insoluble linear polymer ofmonoethylenically unsaturated molecules comprising a nitrogenous monomerR g /R CH2=(1}A(R),. 1N

Where R is H or CH n is an integer having a value of 1 to 2, A is andPatented May 12, 1959 when n is 2, R is a straight or branched chainalkylene group having from 2 to 10 carbon atoms, and R R and R are eachselected individually from the class consisting of H and saturatedaliphatic hydrocarbon groups having from 1 to 10 carbon atoms. Apreferred group is that of amines having the formula Where x may be 2 to10 but is preferably 2 to 5.

Examples of these monomers are:

Acrylamide Methacrylamide N-methyl methacrylamide N-(y-dimethylaminmpropyl methacrylamide N-(fi-dimethylamino) ethylacrylarnide N- (fi-dimethylamino) ethyl methacrylamide IO-aminodecylvinyl ether 8-aminooctyl vinyl ether Diethylaminohexyl methacrylateDiethylaminoethyl vinyl ether 5aminopenty1 vinyl ether 3-aminopropy1vinyl ether Z-aminoethyl vinyl ether Z-aminobutyl vinyl ether4-aminobuty1 vinyl ether 2-aminoethy1 vinyl ether Dimethylaminoethylmethacrylate Dimethylaminoethyl vinyl etherN-3,5,5-trimethylhexyl)aminoethyl vinyl ether N-cyclohexylaminoethylvinyl ether t-Butylaminoethyl acrylate 2-(1,l,3,3-tetramethylbutylamino) ethyl methacrylate N-t-butylaminoethylvinyl ether N-methylaminoethyl vinyl ether N-2-ethylhexylaminoethylvinyl ether N-t-octylaminoethyl vinyl ether It has been found thattextiles colored with pigments carried in a resinous binder derived frompolymers containing at least 1%, and preferably 5% to 25%, by weight ofone of the above monomers are adequately wash-resistant for practicalpurposes. Homopolymers may be used when they are water-insoluble, butcopolymers are most generally useful to produce waterinsoluble polymersinexpensively. These aqueous dispersions may be of high concentration(even up to 70% solids) While remaining low in viscosity so' that higherconcentrations can be readily applied and drying time and effort can begreatly reduced. These dispersions are capable of producing a widevariety of hands from soft to firm or stiff, if desired. Fabrics treatedwith them do not yellow on ageing and their susceptibility to bacterialor fungal attack is not increased by treatment.

The aqueous dispersions may be prepared by emulsifying and thencopolymerizing with the aid of a catalyst a mixture of one or more ofthe monomers specified above alone or in admixture with one or moreother monoethylenically unsaturated copolymerizable monomers such asN-dialkyl acrylamides, e.g., N-dimethyl, -diethyl, -dipropyl, -dibutyl,-diamyl, -dihexyl, and -dioctyl acrylamides; the acrylic, alpha-alkylacrylic and alpha-haloacrylic esters of saturated monohydric alcohols,especially of saturated aliphatic monohydric alcohols, e.g., themethylethyl, propyl, isopropyl, butyl, isobutyl, and amyl esters ofacrylic, methacrylic, ethacrylic, propacrylic, chloro acrylic,bromoacrylic acids; the phenyl, benzyl, and phenylethyl esters of theaforementioned acids; vinyl aromatic compounds, e.g., styrene,alpha-methyl styrene, dimethylstyrenes, dichlorostyrenes, the variouscyanostyrenes, the various methoxystyrenes, vinyl naphthalenes,

e.g., 4-chloro-l-vinyl-naphthalene; vinyl and vinylidene halides, e.g.,vinyl and vinylidene chlorides, bromides, etc-.-; alkyl vinyl ketones,e.g., methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenylketone, etc.; itaconic diesters containing a single CH =C grouping,e.g., the dimethyl, diethyl, dipropyl, dibutyl and other saturatedaliphatic monohydric alcohol diesters of itaconic acid, diphenylitaconate, dibenzyl itaconate, dibenzyl itaconate, di-(phenylethyl)itaconate; vinyl, allyl and methallyl esters of saturated aliphaticmonocarboxylic acids, e.g., vinyl, allyl and methallyl acetates, vinyl,allyl and methallyl propionates, vinyl, allyl and methallyl valerates;vinyl thiophene; 4-vinyl pyridine; vinyl pyrrole; nitriles containing asingle CH =C grouping, e.g., acrylonitrile, methacrylonitrile, etc.Copolymerization by addition to the C =C groups may be assisted by meansofa peroxy catalyst, such as hydrogen peroxide or ammonium persulfate.The emulsification and polymerization may be assisted by a non-ionicemulsifying agent that serves also to stabilize the dispersion of thecopolymer after completion of the copolymerization. The comonomersselected and the proportions thereof should be such as to produce awater-insoluble linear copolymer. The molecular weight of the copolymersmay range from 10,000 to as high as 4,000,000.

Particularly valuable resin dispersions are obtained by thecopolymerization in an emulsion system of at least one of thenitrogenous monomers with one or more monomeric esters of acrylic and/or methacrylic acid in which the alkyl group contains one to eightcarbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, isoamyl, tert-amyl, hexyl, heptyl,n-octyl, Z-ethylhexyl.

The polymerizable emulsions can be prepared at temperatures from toabout 100 C., but intermediate temperatures are much preferred. Thus,with the acrylic esters in which the alkyl group contains one to fourcarbon atoms a temperature from about C. to about 60 C. is employedwhereas a higher temperature; e.g., 30 C. to 80 C., is recommended whenesters contain ing five to eight carbon atoms in the alkyl group arecopolymerized. Peroxidic free-radical catalysts, particularly catalyticsystems of the redox type, are recommended. Such systems, as is wellknown, are combinations of oxidizing agents and reducing agents such asa combination of potassium persulfate and sodium metabisulfate. Othersuitable peroxidic agents include the per-salts such as the alkali metaland ammonium persulfates and perborates, hydrogen peroxide, organichydroperoxides such as tert-butyl hydroperoxide and cumenehydroperoxide, and esters such as tert-butyl perbenzoate. Other reducingagents include water-soluble thiosulfates and hydrosulfites and thesalts, such as the sulfates, of metals which are capable of existing inmore than one valence state such as cobalt, iron, nickel, and copper.The most convenient method of preparing the dispersions of copolymerscomprises agitating an aqueous suspension or emulsion of a mixture ofcopolymerizable monomers and a redox catalytic combination at roomtemperature without the application of external heat. The amount ofcatalyst can vary but for purposes of efficiency from 0.01% to 3.0%,based on the weight of the monomers, of the peroxidic agent and the sameor lower proportions of the reducing agent are recommended. In this way,it is possible to prepare dispersions which contain as little as 1% andas much as 60% or even more of the resinous copolymer on a weight basis.It is, however, more practical and hence preferred, to producedispersions which contain about 30-50% resin-solids.

Any water-insoluble pigment may be used including azo -pigments andlakes, phthalocyanine pigments, vat dye: stuffs in their water-insolubleform, and inorganic pigments such as carbon black, iron oxides, chromeyellows, titanium dioxide and lithopone. Powdered or flaked metals mayalso be included, such as aluminum, bronze,

brass, chromium, or gold. Mixtures may be used if desired.

In addition to the other ingredients, the aqueous dispersions and pastesmay contain a water-soluble thickening agent, such as gum tragacanth,water-soluble cellulose ethers, polyvinyl alcohol or partiallysaponified polyvinyl acetate. The aqueous pastes may contain a mildalkali, for example, sodium acetate, sodium carbonate, chalk, morpholineor ammonia, including, if desired, a mixture of water-soluble substanceswhich form a conventional mildly alkaline buffer. The proportions of theseveral ingredients in the aqueous dispersions and pastes can be variedwidely, and they are adjusted in any convenient manner so that thedispersions or pastes have a consistency suitable forapplication to thefabric by the particular technique to be employed for this purpose.

The ratio of the pigment to the binder is preferably within the range of1:1 to 1:8 by weight but may be higher or lower if desired especially toproduce novelty effects, such as for embossing. The pigment may bedispersed in the aqueous emulsion before polymerization, but ispreferably dispersed into the aqueous polymer dispersion aftercompletionof the polymerization. Similarly, the thickener is preferablyintroduced after polymerization, particularly when a large amountthereof is used for the purpose of rendering the composition of highconsistency to adapt it for printing. The composition may be applied tothe textile in a pad when overall coloring is desired. It may instead beapplied by rolls, particularly printing rolls, when localized coloringis desired. Stencilling or any other system of application may also beresorted to. Generally, regardless of what system is employed, arelatively small increase in weight of the textiles is required in orderto provide adequate coloration thereof. For example, an increase inweight of 1%- 10% in the colored areas may be obtained.

The compositions of the present invention are characteristically aqueousand contain no volatile organic solvent. They accordingly involve nofire hazard, or health hazard as a result of toxicity. Storage and useof the compositions accordingly require the simplest of facilities, noelaborate protective or solvent-recovery systems being required. Theyare also substantially odorless or at the worst, have but a slight,inoffensive odor.

The coloring composition may be applied to textiles of all kinds,including woven, knitted, or other types of textile fabrics, such asfelts. The fibers or yarns of the fab ric may be formed of cotton,rayon, silk, wool, linen; cellulose esters, such as cellulose acetate;proteinaceous types, such as casein, soya bean protein; also linearpolymeric types, such as the polyamides (nylon), polyesters, such aspolyglycol terephthalate (Dacron); and the vinyl types, such aspolyethylene, polyvinyl chloride, polyvinylidene chloride,polyacrylonitrile; copolymers of vinyl chloride with vinyl acetate,acrylonitrile, vinylidene chloride or the like; copolymers of vinylidenechloride with vinyl acetate, ethylene or acrylonitrile; copolymers ofacrylonitrile with vinyl acetate, methacrylonitrile, vinyl pyridines, orwith mixtures of the latter monomers.

The heating required for drying is believed to crosslink the polymerchains and impart insolubility and permanence to the colored fabric.However, in the com position as applied to the fabric, the polymer isessentionally linear in character so that on drying, it is coalescibleinto a film binding the pigment therein. On subsequent heating, thefixation that occurs does not require the addition of a catalyst.Possibly the polymer dispersion may contain acid residues left thereinat the completion of the polymerization. However, a small amount of anacidic catalyst such as ammonium chloride or ptoluene sulfonic acid maybe added to the dispersion, or applied to the treated fabric beforefixation of the polymer thereon by heating, to accelerate cross-linkingthrough the nitrogenous groups or linkages. The colored fabrics arecharacterized by good resistance to washing and cyclic ageing (alternateexposure to light and washing), and practical resistance to crocking.Since the coatings need no external plasticizer to provide flexibility,they do not sufief embrittlement on ageing as a result of loss ofplasticiz'r. v

The aqueous dispersion containing the linear polymer 'or copolymer mayalso be provided with an auxiliary cross-linking agent if it is desiredto enhance the resistance to'washing and when it is desired to renderthe product even more resistant to dry-cleaning. The auxiliarycrosslinking agent is preferably added to the aqueous dispersion orpaste which contains the linear polymer and pigment, although, ifdesired, the pigment may be added after the'cross linking agent has beenincorporated into the polymer dispersion and when a paste is employed,the thickener may be introduced as the finale step in preparation of thecomposition. The proportion of the crosslinking agent that is added issuch that the ratio between the weights of the linear polymer and thecross-linking agent is within the range 6:1 to 1:6 and preferably withinthe range of 5:2 to 2.5. Whether or not an auxiliary cross-linking agentis used, the ratio of the weight of the pigment to the total weight ofbinder (including the crosslinking agent when used) is preferably withinthe range of 1:1 to 1:8. Acidic catalysts, such as pyridinehydrochloride, ammonium chloride, benzyldimethylamine oxalate, arepreferably used with the cross-linking agent (in amounts of about A toabout A2 of the total weight of the aqueous dispersion) but are notessential.

The auxiliary cross-linking agent is an organic compound containing areactive group which is in efl ect bivalent, such as formaldehyde, orcontaining at least two reactive functional groups. For example, theremay be used formaldehyde or dialdehydes, such as glyoxal, andpropandial. There may also be used as a cross-linking agent the lowmolecular weight condensation polymers (which may be of such size as toprevent difiusion into cellulose but are still water-dispersible,including those in acid colloid form) or monomeric reaction products ofan aldehyde, such as formaldehyde, with urea, thiourea, biuret, or otherhomologues or derivatives thereof, such as N,N-ethyleneurea,N,N-ethyleneurea, N,N'-dimethylurea, N,N'-diethylurea,N,N'-dimethoxymethylurea, N,N- dimethoxymethylurea,N,N-diethoxyethylurea, tetramethoxymethylurea, tetraethoxyethylurea.Similar reaction products of formaldehyde with triazines, such asmelamine may also be employed, such as N,N-dimethylmelamine andalcohol-modified melamine-formaldehyde thermosetting resin condensates,e.g., of methyl and ethyl alcohols, for example,dimethoxymethylmonomethylolmelamine. Similar reaction products offormaldehyde with mixtures of triazines with urea, biuret or otherderivatives of urea may be used. Alternatively, diisocyanates, such asmenthane diisocyanate and diepoxides, such as are useful. Similarly,reaction products of formaldehyde with alkyl, alkylene, aralkyl,cycloalkyl, or aryl substitution products of biguanide including those,such as ethylene dibiguanide, in which more than one biguanide radicalisattached to a single organic residue. Such substituted biguanides canbe obtained by the action of dicyandiamide on the hydrochloride of theappropriate alky1-, ara1kyl-, cyclo-alkylor aryl-amine. Primary orsecondary amines can be used. Thus mono-biguanides can be obtained fromdicyandiamide and ethylamine, di-ethylamine, hydroxyethylamine,propylamine, butylamine, 2- hydroxy-propylamine, benzylamine, aniline,toluidines, andmethoxy-anilines, and dibiguanides from ethylenediamine,alpha-beta-diamino-propane, trimethylene diamine, and hexamethylenediamine and other alkylene diamines. I

"(The reaction between dicyandiamide and an amine 6 hydrochloride isconveniently effected by heating at temperatures of the order of ISO-200C. It appears that the reaction often proceeds, at least in part, beyondthe formation of the simple biguanide radical E E since some ammonia isgiven off. Possibly two biguanide radicals lose ammonia with formationof a polyguamde radical such as Other cross-linking agents includepolycarboxylic acids, such as diacids like malonic and succinic acids,also polyacrylic acid, polymethacrylic acid, or copolymers thereof,either water-soluble or water-insoluble, with a catalyst, such aspyridine or benzyldimethylamine.

After application of the aqueous dispersion to the fabric, the latter issubjected to an insolubilization or curing action, such as by drying andheating to a temperature of 180 F. to 350 F. for periods of half aminute to 15 or 30 minutes or more, the higher the temperature used, thelower the time needed in most cases. This curing or baking operationshould be carried on at a temperature below that which causesappreciable deterioration of the fabric material. During the curing ofthe polymer, it apparently cross-links with itself and it is possiblethat it may also react with certain groups of the textile materials,particularly in the case of the cellulosic textiles. When an auxiliarycross-linking agent is present, there is a still further inter-combiningaction that probably occurs. In any event, whatever the reactionsinvolved, there is obtained a highly stable pigmented area.substantially permanently bonded to the textile material. The pig mentedareas are durable against the temperatures encountered during normalusage and also during such washing, dry-cleaning, laundering, andscouring operations as the particular textile material carrying thepigrnented coating is normally subjected.

The following examples are illustrative of the invention:

Example I Anaqueous dispersion of a copolymer is obtained. by theemulsion copolymerization of 92.25 parts by weight of ethyl acrylate and7.75 parts by weight of methacrylamide in the presence of ammoniumpersulfate and sodium hydrosulfite and an ethylene oxide condensationproduct of a t-octylphenol containing from 30 to 50 oxyethylene unitsper molecule as an emulsifier and/or dispersing agent. A pigment(Monastral Fast Blue EFF-a phthalocyanine blue) and water-solublehydroxyethyl cellulose are mixed into the dispersion in such amounts andthe dispersion is diluted to such extent as to produce an aqueousdispersion containing 5% of the copolymer, 2.5% of the pigment, 2% ofthe dispersing agent and 0.05% of the hydroxyethyl cellulose.

A cotton fabric x 80 sheeting) is passed through a padder containing theresulting dispersion to effect overall coloration. vAfter drying at 240F. and then curing at 300 F. for 10 minutes, one portion of the fabricis subjected to a wash test consisting of 40 minutes in 0.1% sodiumstearate at 180? F. while tumbling, followed by several IO-minute rinsesin water. Another portion is partially exposed to light in a fadeometerfor 50 hours and then is washed in the manner just described. The lattertest is a type of cyclic ageing test and serves to detect anydegeneration of the binder under the action of light. Such degeneration,if present, causes the removal of part of the pigment during thesubsequent washing. The dyeing shows good resistance to both washing andcyclic ageing.

, Example II The procedure of Example I was followed except that 7 the.pigment dispersion included 2% of dimethylol-N,N- ethyleneurea and0.25%. of pyridine hydrochloride. The dyeing showed even better washfastness than that of Example I.

Example 111 The; procedure of Example I was followed with a copolymer of95% n-butyl acrylate with dimethylaminoethyl vinyl ether, but thepigment dispersion was applied to a rayon challis. The dyeing shows goodresistance to washing, dry-cleaning and cyclic ageing.

Example V The procedure of Example IV was followed except that thepigment dispersion contained 5% dimethoxymethylurea and /2% of pyridinehydrochloride. The fabric was crease-proofed and stabilized againstshrinkage on washing and the dyeing showed good resistance to washing,dry-cleaning, and cyclic ageing.

Example VI The: procedure of Example I was followed with a copolymer of90% nbutyl acrylate with 1.0% 2-methylaminoethyl vinyl ether. The dyeingshowed good resistance. to washing and cyclic ageing.

Example VII The procedure of Example I. was followed with a copolymer of85 of butoxyethyl acrylate and 15% of 3- dimethylaminopropylacrylamide.Dyeings of good fastmess to washing and cyclic ageing were obtainedExample. VIII The procedure of Example I was followed with a copolymerof 25% N-t-butylaminoethyl vinyl ether, 65% ethyl acrylate and %v vinylacetate except that the pigment was replaced by a corresponding amountof chrome yellow (lead chromate). The dyeings twere fast to washing andcyclic ageing tests.

Example IX The procedure of Example VIII was followed except that afterdrying at 240 F. but before curing at 300 F. the dyed fabric waspassedthrough a 1%. solution of formaldehyde. Similar results were obtained.

Example X The. procedure of Example I was followed with a copolymer of12%. 6-diethylaminohexyl methacrylate, 25% styrene, and 63% n-propylacrylate.

Example XI The procedure of Example X was followed except that the 2.5%blue pigment was replaced with- 1 /z% of chrome yellow and after dryingbut before curing, the fabric was impregnated by a 2% solution ofglyoxal. The fi'nal dyeing showed good fastness to washing, drycleaningand cyclic ageing.

Example XII The procedure of Example I was followed with a copolymer of90% ethyl acrylate and 10% of. 2-(l,1,3,3- tetramethylbutylamino)ethylmethacrylate. Wash-fast dyeing-was obtained.

Example XII] The procedure of Example XII was followed except that 2% ofpolyacrylic acid having a molecular weight of..5;09.Q-and 0.05% of;pyridineihyd'mchlcride 1W61I6 added E5 to the pigment dispersion.Wash-fast dyeing was ob; tained.

The compositions of the present invention may be applied to numeroustypes of substrates, such as paper, paperboard, wallboard, plasteredwalls, metals, woods, leathers, cements, stucco, concrete, and glass forproviding a colored coating thereon. The copolymer may be cured merelyby prolonged standing at room temperature or by heating at elevatedtemperature and the composition may contain auxiliary cross-linkers asdescribed hereinabove.

The polymers or copolymers which contain N-alkyl or N,N-dialkylsubstituted acrylamides or methacrylamides, such as N-butyl acrylamideand N,N-dibutyl acrylamide, are particularly valuable whereverlight-exposure is encountered since it has been found that exposure tolight, whether curing is effected at room temperature or at highertemperatures, improves their color re-retention on subsequent washing. Amodification of the process may include exposure to light, preferably ofhigh intensity, and especially in the ultraviolet region before, during,or after curing. This characteristic renders these particular polymersespecially valuable for wall paints and automotive-type paints, as wellas textile. finishes, since exposure to the sun improves the permanenceof the pigment-binding characteristics thereof.

It is to be understood that changes and variations may be made withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

We claim:

1. A method for coloring a textile material comprising the steps ofapplying to a textile fabric an. aqueous composition containing about A%to /z% by weight of an acidic catalyst and comprising a water-insolublepigment intimately mixed with a binder consisting essentially of (a) awater-insoluble linear polymer of a mixture consisting of (1) from 1% to25 by weight of a: monomer having the general formula GHQ-O (R)0ON\ R3where R is selected from the group consisting ofI-I and CH and R and Rare each selected individually from the class consisting of H andsaturated aliphatic hydro carbon radicals having from 1 to 10 carbonatoms, with (2) 99% to by weight respectively of at least one alkylester of an acid selected from the group. consisting of acrylic and.methacrylic acids in which thealkyl group contains 1 to 4 carbon atoms,and (b) a cross-linking agent selected from the group-consisting ofreaction products of formaldehyde with a member selectedfromthe classconsisting of N,N'-ethyleneurea and melamine, the cross-linker beingdissolved in the: aqueous composition and the pigment and copolymerbeing dispersed therein, the ratio of the weights of the copolymer tothe crosslinker being from 6:1 to 1:6 and the. ratio of the weights ofbinder to pigment being from 1:1 to 8:1, and then drying and heating thefabric at a temperature of. F. to- 350 F. for a period of ahalf-minute-to about thirty minutes, the longer time being usedat thelower tem. perature.

2. As an article. of manufacture a textile fabric obtained by theprocess of claim 1.

3. A method as defined in claim 1 in which. the. com position is in theform of aprintable paste containing-a water-soluble polymeric thickener.

4'. A method as defined in claim 1 in which the'monomer ismethacrylamide.

5. A method as defined in claim 1 in which'the binder comprises acopolymer of methacrylamide: withethyl acrylate.

6. A. method as defined in claim 1 in which the binder comprises acopolymer of methacrylamide with. ethyl acrylate in theproportionofaboutv 92 to 8 respectively.

7. A method for coloring a textile material comprising the steps ofapplying to a textile fabric an aqueous composition containing about to/z% by weight of an acidic catalyst, and about 2 /z% by weight of awaterinsoluble pigment intimately mixed with a binder consistingessentially of (a) a water-insoluble copolymer of a mixture consistingof (1) from 5% to 25% by weight of methacrylamide with (2) 95% to 75% byweight respectively of an alkyl ester of an acid selected from the groupconsisting of acrylic acid and methacrylic acid in which the alkyl groupcontains 1 to 4 carbon atoms, and (b) a cross-linking agent selectedfrom the group consisting of reaction products of formaldehyde withN,N-ethyleneurea and melamine, the cross-linker being dissolved in theaqueous composition and the pigment and copolymer being dispersedtherein, the ratio of the weights of the copolymer to the cross-linkingagent being from 6:1 to 1:6 and the ratio of the weights of binder topigment being from 1:1 to 8:1, and subsequently drying and heating thefabric at a temperature of 180 F. to 350 F. for a period of ahalf-minute to about thirty minutes, a time of longer duration in theaforesaid time range being used when a temperature in the lower portionof the temperature range is given.

8. A method as defined in claim 7 in which the binder References Citedin the file of this patent UNITED STATES PATENTS 2,173,005 Strain Sept.12, 1939 2,511,113 La Piana et a1. June 13, 1950 2,600,783 Kropa June17, 1952 2,653,140 Allenby et al Sept. 22, 1953 2,680,110 Loughran eta1. June 1, 1954 2,689,844 Melamed Sept. 21, 1954 2,780,567 Kline et al.Feb. 5, 1957 FOREIGN PATENTS 898,408 France July 3, 1944

1. A METHOD FOR COLORING A TEXTILE MATERIAL COMPRISING THE STEPS OFAPPLYING TO A TEXTILE FABRIC AN AQUEOUS COMPOSITION CONTAINING ABOUT1/4% TO 1/2% BY WEIGHT OF AN ACIDIC CATALYST AND COMPRISING AWATER-INSOLUBLE PIGMENT INTIMATELY MIXED WITH A BINDER CONSISTINGESSENTIALLY OF (A) A WATER-INSOLUBLE LINEAR POLYMER OF A MIXTURECONSISTING OF (1) FROM 1% TO 25% BY WEIGHT OF AMONOMER HAVING THEGENERAL FORMULA